This study presents a bioinspired dinickel catalyst, Ni²⁺Ni²⁺(bphpp)(AcO)₂, for the efficient electrocatalytic reduction of CO₂ to CO. Inspired by the NiFe-CODH enzyme, the catalyst features a redox-active phenanthroline ligand and a secondary Ni site, which facilitate electron transfer and C–O bond activation. The dinickel complex exhibits a significantly higher reactivity compared to a mononuclear Ni catalyst, with a turnover frequency (TOF) of 20.5 s⁻¹, which is approximately five times higher than that of the mononuclear Ni catalyst. Electrochemical and computational studies reveal that the redox-active phenanthroline modulates electron injection and transfer, similar to the [Fe₃S₄] cluster in NiFe-CODH, while the secondary Ni site promotes C–O bond activation and cleavage through electron mediation and Lewis acid characteristics. The catalyst demonstrates high efficiency in CO₂ reduction, with a half-wave potential of -2.25 V and a Faradaic Efficiency (FE) of 91% for CO production. The study highlights the importance of bimetallic cooperation in CO₂ reduction catalysis, emphasizing the role of the secondary Ni site in facilitating electron transfer and C–O bond cleavage. The results suggest that the dinickel catalyst is a promising candidate for the development of efficient CO₂ reduction catalysts, with potential applications in carbon capture and utilization. The work provides valuable insights into the design of bimetallic catalysts for CO₂ reduction, demonstrating the effectiveness of redox-active ligands and bimetallic cooperation in enhancing catalytic activity.This study presents a bioinspired dinickel catalyst, Ni²⁺Ni²⁺(bphpp)(AcO)₂, for the efficient electrocatalytic reduction of CO₂ to CO. Inspired by the NiFe-CODH enzyme, the catalyst features a redox-active phenanthroline ligand and a secondary Ni site, which facilitate electron transfer and C–O bond activation. The dinickel complex exhibits a significantly higher reactivity compared to a mononuclear Ni catalyst, with a turnover frequency (TOF) of 20.5 s⁻¹, which is approximately five times higher than that of the mononuclear Ni catalyst. Electrochemical and computational studies reveal that the redox-active phenanthroline modulates electron injection and transfer, similar to the [Fe₃S₄] cluster in NiFe-CODH, while the secondary Ni site promotes C–O bond activation and cleavage through electron mediation and Lewis acid characteristics. The catalyst demonstrates high efficiency in CO₂ reduction, with a half-wave potential of -2.25 V and a Faradaic Efficiency (FE) of 91% for CO production. The study highlights the importance of bimetallic cooperation in CO₂ reduction catalysis, emphasizing the role of the secondary Ni site in facilitating electron transfer and C–O bond cleavage. The results suggest that the dinickel catalyst is a promising candidate for the development of efficient CO₂ reduction catalysts, with potential applications in carbon capture and utilization. The work provides valuable insights into the design of bimetallic catalysts for CO₂ reduction, demonstrating the effectiveness of redox-active ligands and bimetallic cooperation in enhancing catalytic activity.